负载碳酸钠煤焦催化气化反应特性研究

李献宇; 郭庆华; 丁路; 于广锁

负载碳酸钠煤焦催化气化反应特性研究

李献宇^{1, 2},
郭庆华^{1, 2},
丁路^{1, 2},
于广锁^{1, 2, ,}

1.
华东理工大学煤气化及能源化工教育部重点实验室, 上海 200237
2.
上海市煤气化工程技术研究中心, 上海 200237

基金项目:

国家自然科学基金 21376081

详细信息

中图分类号: TQ546
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- 被引次数: 0
出版历程
- 收稿日期: 2016-08-23
- 修回日期: 2016-10-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-12-10

Investigation on catalytic gasification reaction characteristics of coal char with Na₂CO₃

LI Xian-yu^{1, 2},
GUO Qing-hua^{1, 2},
DING Lu^{1, 2},
YU Guang-suo^{1, 2
, ,}

1.
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China
2.
Shanghai Engineering Research Center of Coal Gasification, Shanghai 200237, China

More Information

Corresponding author: Tel: 021-64252974, Fax: 021-64251312, gsyu@ecust.edu.cn

摘要

摘要: 基于热重分析仪开展负载碳酸钠神府烟煤/遵义无烟煤煤焦气化实验，并借助扫描电子显微镜和孔结构及比表面积分析仪表征焦样孔结构及表观结构变化，考察了反应温度（650-800℃）、气化剂（水蒸气、二氧化碳）及碳酸钠负载量（钠离子负载量2.2%、4.4%、6.6%，质量分数）对神府烟煤/遵义无烟煤焦样气化反应活性的影响。结果表明，碳酸钠有利于促进神府/遵义煤热解过程孔隙结构的发展。在二氧化碳气氛下，适宜催化剂负载量使神府烟煤反应活性提高，过多负载催化剂堵塞煤焦内部孔隙结构，使得气化反应活性降低，遵义无烟煤反应活性随负载量增加而提高，两者反应活性均随温度升高而提高。在水蒸气气氛下，神府烟煤/遵义无烟煤在一定条件下反应活性随催化剂负载量增大、温度升高而提高。碳酸钠的添加能够在保证气化反应性的前提下降低气化反应温度和活化能。
- 碳酸钠 /
- 催化气化 /
- 孔隙结构 /
- 反应活性
Abstract: The coal char gasification experiments with Na₂CO₃ as catalyst was investigated on TGA. The pore structure and apparent structure evolution characteristics of char were studied by scanning electron microscopy and pore structure and specific surface area analyzer. The influence of temperature (650-800℃), gasification agent (steam, CO₂) and sodium carbonate loadings (Na⁺ loading amounts 2.2%, 4.4%, 6.6%) on the gasification reactivity of Shenfu bituminous coal (SF) and Zunyi anthracite (ZY) were investigated. The results show that the loading of Na₂CO₃ stimulates the development of pore structure in pyrolysis process. In the atmosphere of CO₂, there was a saturated catalyst capacity for SF and excessive catalyst loading could block internal pore structure of coal, leading to the decrease of gasification reactivity. ZY gasification reactivity increases with catalyst loading, and both SF and ZY gasification reactivity increase with the increase of temperature. In the atmosphere of steam, both SF and ZY gasification reactivity increase with the rise of catalyst loading and temperature. Na₂CO₃ is favorable for the decrease of reaction temperature and activation energy under the desired gasification rate.
- Na₂CO₃ /
- catalytic gasification /
- pore structure /
- reactivity

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图 1 负载碳酸钠煤/煤焦电镜照片

Figure 1 SEM photographs of coal/char mixed with Na₂CO₃

(a): SF-raw-4.4Na; (b): SF-4.4Na-800P; (c): SF-raw-6.6Na; (d): SF-6.6Na-800P; (e): ZY-raw-4.4Na; (f): ZY-4.4Na-800P; (g): ZY-raw-6.6Na; (h): ZY-6.6Na-800P; 1, 2, 3: different surface area of coal/char

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图 2 神府/遵义样品催化和非催化气化反应性比较

Figure 2 Gasification reactivity comparison of SF/ZY coal with and without Na₂CO₃

(a): 650℃-CO₂ gasification; (b): 700℃-CO₂ gasification; (c): 750℃-CO₂ gasification; (d): 800℃-CO₂ gasification ■: SF-raw-800P; □: SF-2.2Na-800P; ▲: SF-4.4Na-800P; △: SF-6.6Na-800P; ▼: ZY-raw-800P; ▽: ZY-2.2Na-800P; ●: ZY-4.4Na-800P; ○: ZY-6.6Na-800P

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图 3 神府/遵义样品催化和非催化气化反应性比较

Figure 3 Gasification reactivity comparison of SF and ZY coal with and without Na₂CO₃

(a): 650℃-H₂O gasification; (b): 700℃-H₂O gasification; (c): 750℃-H₂O gasification; (d): 800℃-H₂O gasification ■: SF-raw-800P; □: SF-2.2Na-800P; ▲: SF-4.4Na-800P; △: SF-6.6Na-800P; ▼: ZY-raw-800P; ▽: ZY-2.2Na-800P; ●: ZY-4.4Na-800P; ○: ZY-6.6Na-800P

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图 4 神府烟煤和遵义无烟煤不同气化温度下初始反应速率

Figure 4 Initial reaction rate (R₀) of SF and ZY samples at different gasification temperatures

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图 5 神府和遵义样品的Arrhenius曲线

Figure 5 Arrhenius curves of SF (a) and ZY (b) samples

■: SF-2.2Na-800P-CO₂; ●: SF-4.4Na-800P-CO₂; ▲: SF-6.6Na-800P-CO₂; : ZY-2.2Na-800P-CO₂; : ZY-4.4Na-800P-CO₂; : ZY-6.6Na-800P-CO₂

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表 1 样品的煤质分析

Table 1 Characteristic data of tested coal samples

Sample	Proximate analysis w_d /%			Ultimate analysis w_d/%					Ash fusion temperature t/℃
Sample	V	FC	A	C	H	N	S	O	DT	ST	HT	FT
SF	35.42	58.29	6.29	79.14	2.32	1.12	0.77	10.36	1152	1167	1175	1179
ZY	7.59	73.46	18.95	76.57	2.13	1.10	0.83	0.42	1345	1370	1395	1463

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表 2 原料的主要灰组分

Table 2 The main ash compositions of raw materials

Sample	Composition w/%
Sample	SiO₂	Al₂O₃	Fe₂O₃	CaO	Na₂O	K₂O	MgO
SF	33.36	12.44	9.11	27.78	1.73	0.67	1.34
ZY	43.05	20.78	21.43	7.42	0.86	0.52	2.90

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表 3 负载碳酸钠煤/煤焦表面的元素组成

Table 3 Elemental composition of coal/char with or without Na₂CO₃

Contact surface	Composition w/%			Contact surface	Composition w/%
Contact surface	C	O	Na	Contact surface	C	O	Na
SF-raw-4.4Na-1	29.5	30.3	22.5	ZY-raw-4.4Na-1	33.2	40.5	8.5
SF-raw-4.4Na-2	48.5	25.2	7.0	ZY-raw-4.4Na-2	37.5	18.2	18.0
SF-raw-4.4Na-3	46.3	26.6	8.0	ZY-raw-4.4Na-3	38.2	34.5	18.1
SF-4.4Na-800P-1	51.3	24.5	7.3	ZY-4.4Na-800P-1	10.3	41.6	23.8
SF-4.4Na-800P-2	25.3	25.6	32.3	ZY-4.4Na-800P-2	18.3	4.6	12.9
SF-4.4Na-800P-3	7.5	3.9	8.1	ZY-4.4Na-800P-3	7.8	43.2	25.2
SF-raw-6.6Na-1	28.6	27.6	30.5	ZY-raw-6.6Na-1	30.7	41.6	5.7
SF-raw-6.6Na-2	32.5	24.8	20.7	ZY-raw-6.6Na-2	30.6	19.5	20.3
SF-raw-6.6Na-3	28.0	13.7	17.9	ZY-raw-6.6Na-3	35.7	17.3	19.6
SF-6.6Na-800P-1	6.9	5.4	20.5	ZY-6.6Na-800P-1	11.5	30.5	24.9
SF-6.6Na-800P-2	14.5	13.8	6.7	ZY-6.6Na-800P-2	16.8	26.8	20.6
SF-6.6Na-800P-3	20.7	28.9	12.6	ZY-6.6Na-800P-3	19.5	30.8	16.9
note: SF-raw-4.4Na-1 is the surface area of 1# in SF-raw-4.4Na

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表 4 氮气吸附法测定的样品孔结构参数

Table 4 Pore structure parameters of samples measured by N₂ gas adsorption analysis

Sample	A_BET /(m²·g^-1)	Pore volume v/ (cm³·g^-1)
SF-raw-800P	2.2070	0.0014
SF-4.4Na-800P	17.2330	0.0195
SF-6.6Na-800P	2.9011	0.0064
ZY-raw-800P	1.6845	0.0052
ZY-4.4Na-800P	1.8891	0.0076
ZY-6.6Na-800P	1.7665	0.0067

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表 5 煤/煤焦的水溶性和离子交换型钠元素含量

Table 5 Water-soluble and ion-exchanged Na contents in coal/char

Coal/char	Actual loading of sodium w/%	Theoretical loading of sodium w/%
SF-raw-2.2Na	1.9	2.2
SF-raw-4.4Na	4.3	4.4
SF-raw-6.6Na	6.3	6.6
SF-2.2Na-800P	1.3	2.2
SF-4.4Na-800P	3.7	4.4
SF-6.6Na-800P	5.7	6.6
ZY-raw-2.2Na	2.1	2.2
ZY-raw-4.4Na	4.3	4.4
ZY-raw-6.6Na	6.4	6.6
ZY-2.2Na-800P	1.1	2.2
ZY-4.4Na-800P	2.1	4.4
ZY-6.6Na-800P	4.3	6.6

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表 6 神府和遵义样品的动力学参数

Table 6 Kinetic parameters of SF and ZY samples

Sample	E_a/(kJ·mol^-1)	lnA
SF-2.2Na-800P-CO₂	142.8	14.5623
SF-4.4Na-800P-CO₂	106.1	10.4127
SF-6.6Na-800P-CO₂	120.3	12.7232
ZY-2.2Na-800P-CO₂	150.1	15.4361
ZY-4.4Na-800P-CO₂	133.1	11.9361
ZY-6.6Na-800P-CO₂	104.7	7.4310
SF-2.2Na-800P-H₂O	126.3	12.7423
SF-4.4Na-800P-H₂O	111.2	11.5243
SF-6.6Na-800P-H₂O	95.3	9.4760
ZY-2.2Na-800P-H₂O	121.2	12.4653
ZY-4.4Na-800P-H₂O	102.3	10.7434
ZY-6.6Na-800P-H₂O	86.4	8.5263

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